Pilot plant synthesis of triaminotrinitrobenzene (TATB) from a novel process

Sharon Dressen, Douglas Merrill, Andrew Sanderson, Stephen Velarde*

Approved for public release by NSWC-Indian Head, 21September 2004

Prepared For2004 IM/EM Technical Symposium

November 15-17, 2004 San Francisco, CA

ATK THIOKOL INC.

Outline

Novel TATB processDriving force behind developmentProcess overview

Process resultsNitrationAlkylationAmmonolysis

Conclusions

ATK THIOKOL INC.

Acknowledgements

The funding for this work was provided to ATK Thiokol bythe US Navy ManTech officeSpecial thanks to Lori Nock, Al Stern, Chuck Painter, JerrySalan, Tim Mahoney, John Brough (Navy), George Boyd(Andrulis), and Rob Schmidt, Alex Mitchell, Mike Coburn(DOE)

ATK THIOKOL INC.

Why TATB Synthesis?

Current production method produces undesirablewaste (trichlorobenzene route)Future supplies of TCB uncertain – could become amajor cost driver for future TATB productionDevelopment of an alternate route to ensureuninterrupted supply of TATB for needed applications

environmentally acceptable waste streamscost-competitive product (vs. current TATB)uncomplicated and robust process to be crediblytransitioned to production

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TATB AdvantagesTATB could be utilized as a valuable material for achieving IMcompliance

High density - 1.93 g/cm3

High thermal stabilityLow shock sensitivity

TATB is already qualified in a number of systems

735050TATB

690015TNT

87507.5RDX

76000.2Nitroglycerine

Confined detonation velocity(m/s)

Impact sensitivity (N m)Compound

Source: Rudolf Meyer, Explosives (3rd edition), 1987, VHC Publishers, New York.

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Alternate TATB Process Overview

OH

OH

HO

phloroglucinol

nitration OH

OH

HONO2

NO2O2N

1. protection2. ammonia

NH2

NH2

H2NNO2

NO2O2N

TATB

Three-step process was proposed starting from phloroglucinolphloroglucinol found in naturally-occuring glycoside derivativesworldwide, approximately 140-200 metric tons of phloroglucinol areproduced each yearnumerous synthetic industrial routes (including demil of TNT)

Proposed process first reported in UK by Bellamy, Golding and WardConsiderable route development performed at ATK Thiokol

necessary for scale-up consideration

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TATB Transition to Scale-Up

Lab scale1 g to <1000 gmultiple laboratoryfume hoods5, 10, 22-L reactors(kilo bays)

Kilogram scalemultiple kilogramsdedicated facilityincluding remoteoperation capability50-L, 5 gallon reactorsfor batch processesloop reactor andcontinuous reactorset-up for continuousoperation

Pilot facility100’s lbs.20, 50, 200, 500-gallon reactorsremote operationsdedicated operators

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Nitration

OH

OH

HO OH

OH

HONO2

NO2O2N1. NaNO2, NaOH2. HNO3, 5oC3. heat

Phloroglucinol TNPG

Reaction exotherm easy tocontrolOver 1,000 lbs. (450 kg) ofTNPG producedReaction yields have beengreatly improved (from ~ 75%to >92%)

excellent scalability andreproducibility

1.86 J (mass ignition @8 J)

Electrostatic discharge

800 @ 8 ft/sABL friction (lbs)

1.8ABL impact (cm)

TNPGSafety TestSmall scale safety data

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Alkylation

OH

OH

HONO2

NO2O2N

OR

OR

RONO2

NO2O2N

(RO)3CH

TNPG TETNB

Efficient, straightforwardprocessHigh reactor loading levelsIsolated yields >90%Triethylorthoformate used forcost considerationsTETNB relatively insensitiveand easy to handle

R = Me, Et, or Pr

>8 JElectrostatic discharge

800 @ 8 ft/sABL friction (lbs)

64ABL impact (cm)

TETNBSafety Test

Small scale safety data

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Ammonolysis

OR

OR

RONO2

NO2O2N

NH2

NH2

H2NNO2

NO2O2N

NH3, solvent

TATBTETNB

2.7 J (no mass ignition)Electrostatic discharge

800 @ 8 ft/sABL friction (lbs)

80ABL impact (cm)

TATBSafety Test

Small scale safety data

Simple process that can yieldcomplicated results

particle size & shape, purity

Target particle size 40-60micron (to match currentTATB spec)Yield generally >98%

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18.5, 24.6, 35.4590-04-0158

2.9, 4.3, 6.8346-04-005

Particle size (µm)(10, 50, 90%)

Lot number

60.5, 82.6, 142.9346-04-012

21.6, 31.2, 59.6346-04-011

37.1, 54.1, 105.0346-04-010

42.2, 65.1, 131.3346-04-009

18.7, 26.6, 49.0346-04-008

21.7, 33.2, 65.0346-04-007

32.7, 42.4, 71.8346-04-006

18.9, 21.9, 25.6346-04-001

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TATBPurity determination was a concern due to TATB insolubilityHPLC/MS used to identify impurities

ammonium diaminopicrate and 1-ethoxy-3,5-diamino-2,4,6-trinitrobenzene are process impuritiesquantification of impurities by HPLC an approximation due tosimilar absorbance spectraTATB produced generally 95-99% pure

nm200 250 300 350 400 450 500 550

mAU

0

25

50

75

100

125

150

175

200

DAD1, 11.121 (224 mAU,Apx) of 082-0201.D

nm200 250 300 350 400 450 500 550

mAU

0

5

10

15

20

25

30

DAD1, 3.636 (33.6 mAU,Apx) of 083-0301.D

UV spectrum of TATB UV spectrum of ADAP

NO2

NO2

O2NONH4

NH2H2N

NH2

NH2

H2NNO2

NO2O2N

ATK THIOKOL INC.

TATB Thermal Behavior

Decomposition onset at 370°C

TATB possesses excellent thermal stability

ATK THIOKOL INC.

ConclusionsA novel process for producing TATB from phloroglucinol hasbeen successfully transitioned from the lab to the pilot plant level

The three step process reduces the environmental impact ofTATB production when compared to the traditionaltrichlorobenzene route

TATB particle size control possible via the current route

The TATB produced under this effort will undergo extensivetesting and evaluation at the completion of the program